Htdboabomatic alcohol



Patented Jan. 7, 1936 UNITED, s ATss PATENT OFFICE r 2,020,668 maosaommc ALCOHOL Herman Alexander Brnson and Lloyd W. Covert, rhlladelphia, Pa., asslgnors to Biihm & Haas Company, Philadelphia, Pa.

No i i-swing. Application October 21. 1934.

Serial No. 750,279

15 Claims. (Cl. 260-153) This invention relates to hydrogenation products of nuclear tertiary alkylated phenols having at least 8 carbon atoms in the tertiary alkyl group; said hydrogenation products being new compounds consisting of hydroaromatic second-v ary alcohols containing a nuclear tertiary alkyl group of at least 8 carbon atoms.

More particularly this invention deals with the preparation of wax-like or viscous, oily bodies by 10 the nuclear hydrogenation of the m'onohydric orpolyhydric phenols obtained by condensing tertiary olefines having at least 8 carbon atoms wig: phenols and acid-catalysts such as sulfuric ac Q 5 We have found namely, that the tertiary alkyl phenols such .as' i my-tetramethylbutylphenol, tertiary-iso-duodecylphenol, "tertiary-iso-hexadecylphenol and the corresponding cresols,

xylenols, resorcinols, guaiacols, and naphthols, obtainable respectively from the tertiary oleiines such as di-isobutylene, tri-isobutylene, tetra -isobutylene, beta-dibutylene, and di-isoamylene, by condensation with phenols in the presence of acidic catalysts, preferably sulfuric acid; upon tlitreatment with hydrogen under high pressure- 7 and at elevated temperatures in the presence of active, finely divided hydrogenation catalysts such as finely divided nickel, give the correspondingnuclear tertiary alkyl hydroaromatic secn ondary alcohols having very'useful, and in many cases, novel properties. For example, they are colorless, practically odorless liquids or low melting waxes which are insoluble in water but readily soluble in petroleum oils, fatty'glycerides, and in most organic solvents. Moreover they are miscible and compatiblewith'a great many org anic plastic materials such as rubber, paraiiin,

natural and synthetic resins, cellulose esters and 40 cellulose ethers. Because of their high boiling points, low vaporgpressure, pale color, light-fast- .ness, freedom rancidlty, they are useful a plasticizers for coating and molding fio npositions, and as lubricants for textile fibres "or for ,ilne m such as watches. ,Qhemically they are useful-as intermediates for preparing long-chain-tertiary alkyl adipic acids by oxidation with nitric acid for example; also in preparing esters, or as dyestufl intermediates. They are useful as softening agents in rubber compounds, and as ingredients for cosmetics, soaps, and insecticides. s 4

In order to illustrate the preparation-of these bodies, the followingexamplesare givenr Example 1 (A) 200 grams of 41,:7/1'tfitlfllllthYlblltYlPhQ- nol made by condensing di-isobutylene with phenol in the presence of concentrated sulfuric acid) was mixed with 15 grams of active, finely divided 5 nickel, and heated in 'a shaking autoclave with hydrogen under pressure at 200 C. for 4 hours. The pressure was 3100 lbs. per square inch. The product a, y tetramethylbutylcyclohex anol' was a colorless, waxy, crystalline compound melting at 56 C. andboiling at 140-142 C/6.5

(B) A. 50% solution of ann-tetramethylbutylphenol in alcohol was passed together 15 with hydrogen, over 300 com. of supported nickel catalyst in a steel chamber, at a rate of approximately 50 grams per hour at a temperature of 250 C., and a pressure of 3100 lbs. per square inch. The said phenol was hydrogenated in a 20 few hours. v I

Example 2 The condensation product of phenol and triisobutylene, made with concentrated sulfuric acid as a catalyst and, herein referred to as tertiary- 25 iso-duodecylphenol, was hydrogenated under the same conditions as described Example 10.).

The product, tertiary-iso-duodecyl cyclohexanol, was a colorless, viscous oil,boiling at 180-200 C/10 mm; p 80 Example 3 A condensation product of phenol and commercial tetra-isobutylene of boiling range 0/3 mm. said product being a mixture of 35 tertiary-iso-hexadecylphenols melting at 40-50 0., was\hydregenated as described in Example 1(A). The product; a technical mixture of tertiary -iso-hexadecylcyclohexanols was a viscous colorless oil whichsolidifled to a waxy mass.

Example 4 drogenation of the above tertiary ainlphenols is 100 to 250 C. under a working pressure of 1000 to 3500 lbs. per square inch.

The term p heno referred to broadly herein includes polynuclear as well as monocycllc nuclear hydroxy or polyhydroxy aromatic compounds. The alpha, alpha, gamma, gamma tetramethylbutyl group refers to the group derived from (ii-isobutylene. The a, a, 'y, 'y-tetramethylbutylcyclohexanols, particularly are use- Iul as plasticizers for molding resins of the phenol-formaldehyde type since they are colorless, inert to alkalies, or dilute acids, and powerful softeners for this type of resin. They are also eflicient as plasticizers for nitrocellulose.

We claim:-

1. A process which comprises heating a tertiary alkyl-phenol having at least 8 carbon atoms in the tertiary alkyl group, with fineLv divided active nickel, in the presence or hydrogen under pressure in a substantially neutral medium.

2. A process which comprises heating a tertiary alkylphenol having at least 8 carbon atoms inthe tertiary alkyl group, with an active bydrogenation catalyst in the presence of hydrogen under pressure in a substantiallyneutral medium.

,3. A process which comprises heating a tertiary alhlphenol with finely divided active nickel in the presence or hydrogen under pressure; said tertiary alkylphenol being a nuclear condensation product of a phenol and a polymer 0! isobutylene in a substantially neutral medium.

4. A process which comprises heating a tertiary alkylphenol having at least 8 carbon atoms in the tertiary alkyl group, with fineLv divided active nickel in the presence of hydrogen at about 200 C. and 3100 lbs. per square inch pressure in a substantially neutral medium.

nickel, in the presence of hydrogen under pressure. 15

8. A process which comprises heating alpha, f alpha, gamma, gamma-tetramethylbutyl-cresol with finely divided active nickel in the presence of hydrogen under pressure. a

9. Alpha, alpha, gamma, gamma, tetramethyl- 20 butylcyclohexanol.

10. Alpha, alpha, gamma, gamma, tetramethylbutylmethylcyclohexanol.

11. Tertiary-isoduodecylcyclohexanol, in which the tertiary-isoduodecyl group is derived from 25 tri-isobutylene.

12. ,A hydroaromatic secondary alcohol containing a nuclear tertiary alkyl group of at least 8 carbon atoms.

13. A hydroaromatic secondary alcohol con- 30 taining a nuclear tertiary alkyl group derived from a polymer of isobutylene.

14. A hydroaromatic secondary alcohol containing as a nuclear tertiary alkyl group, the alpha, alpha, gamma, gamma, tetramethylbutyl group.

' l5.'-A hydroaromatic secondary alcohol containing as a nuclear tertiary alkyl group, the tertiary radical corresponding to tri-isobutylene.

\ mum ALEXANDER BRUSON. morn w. COVERT. 

